JPH11186571A - Non-monocrystalline photosemiconductor, its manufacturing method and electrophotographic photosensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make an infrared absorption spectrum not to change, even if a nitrogen based III-V compound semiconductor is left as it is, in the outer atmosphere for a long-term period by a method wherein a coupling state of an element included in a film and hydrogen is controlled therein. SOLUTION: The ratio of the degree of extinction between an absorption peak showing coupling of nitrogen and hydrogen of an infrared absorption spectrum of a non-monocrystalline photosemiconductor and an absorption peak showing the coupling of carbon and hydrogen is 3 or more, and the ratio of the degree of extinction between an absorption peak showing coupling of nitrogen and hydrogen and an absorption peak showing coupling of a III element and hydrogen is made 0.05 or more. The ratio of the degree of extinction between an absorption peak showing the coupling of III group element and nitrogen and an absorption peak showing the coupling of the III group element and hydrogen is 1.5 or more, and the absorption peak is an absorption band of a unitary form, and a halfvalue width of the absorption peak is set to 250 cm or less. By satisfying these conditions, even if the semiconductor is left standing as in the air for a long-term period, the infrared absorption spectrum is made not to change.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical semiconductor for electronics, and more particularly, to a new non-single-crystal optical semiconductor suitable for an excellent optical semiconductor, a method of manufacturing the same, and a method using the same. The present invention relates to an optical semiconductor device.

[0002]

2. Description of the Related Art Conventionally, an amorphous or microcrystalline non-single-crystal optical semiconductor has been used as a photoelectric conversion member for a semiconductor light receiving element. For example, amorphous chalcogenide compounds such as selenium and tellurium are widely used in image pickup tubes, light receiving elements, electrophotographic photoreceptors, and the like (Ohm, “Basics of amorphous semiconductors”). In recent years, hydrogenated amorphous silicon has been used in solar cells, image sensors,
Used for lm Transistor, electrophotographic photoreceptor, etc.

However, conventional non-single-crystal optical semiconductors formed from an amorphous chalcogenide compound or hydrogenated amorphous silicon have various problems. Amorphous chalcogenide compounds are unstable with respect to heat, are easily crystallized, have limited conditions for use, and have drawbacks such as inability to control valence electrons. In addition, in hydrogenated amorphous silicon, valence electrons can be controlled, a pn junction and an electric field effect at the interface can be realized, and the heat resistance is up to about 250 ° C. Yes (Staebler-Wronski effect: Applied physics handbook, etc.), for example, there is a problem that the efficiency of the solar cell is reduced during use. Furthermore, the band gap of amorphous or microcrystalline silicon is about 1.7 eV to 1.5 eV, and it is necessary to add Ge and C so that sunlight can be used effectively and sufficient light can reach the active region. Although the band gap can be narrowed or widened, even if these elements are added and changed by about 3 eV, there is a problem that the photoconductive property is greatly deteriorated and light in a wide range cannot be used effectively. Further, a semiconductor containing an element such as Ge or C has a crystal of an indirect transition type, cannot be used for a light-emitting element, and has a limited use.

In recent years, one of the greatest environmental problems on the earth is an increase in the amount of ultraviolet rays on the ground due to destruction of the ozone layer. For this reason, what is called a solar blind type ultraviolet light receiving element capable of measuring the amount of ultraviolet light even in a bright place is desired. [M. Razeghi and A. Rogalski, J. Ap
pl.Physics, 79 (1996) 7466]. Furthermore, a wavelength-separated light-receiving element that can easily measure the ratio to the total light amount of all wavelengths, including the effects of seasonal fluctuations and weather fluctuations, is desired.
None of them had high sensitivity, could respond at high speed with low dark current, and had excellent weather resistance such as humidity and temperature. Conventionally, optical semiconductors are widely used in colorimetric devices.For example, the sensitivity at short wavelengths is significantly reduced in Si and the like, and it is necessary to take a method such as scintillation in the ultraviolet region or the like. There was a problem that it became complicated.

On the other hand, most of the III-V group compound semiconductors belong to direct transition type semiconductors, and have a characteristic that the light absorption coefficient is large and the band gap can be changed by the composition. In particular, the nitrogen-based compound is GaN eGaN from 1.9 eV.
Up to 3.2 eV, and up to 6.5 eV of AlN, the band gap can be changed widely from the ultraviolet region to the visible region. Therefore, as a non-single-crystal optical semiconductor whose band gap can be freely set, a non-single-crystal optical semiconductor composed of a III-V compound, particularly a non-single-crystal optical semiconductor composed of a nitrogen-based III-V compound is expected. Have been.

However, nitrogen-based III-V compound semiconductors are generally grown using sapphire, GaAs and SiC substrates as substrates, but these substrates are expensive and have a lattice constant. Since they are not compatible with these semiconductors, crystal growth cannot be performed as they are, and a buffer layer is inserted or a substrate is nitrided. This crystal growth is usually performed at a temperature of 800-1100 ° C. However, materials compatible with such high temperatures are limited, and the size of the bulk crystal for the substrate is limited, so that a film with an arbitrary large area can be obtained. There was a problem that can not be.
In addition, many light input / output materials have insufficient light transmissivity, and materials having good light transmissivity are insulative. For this reason, amorphous or microcrystalline materials are suitable for two-dimensional devices having a relatively large area, but non-single-crystal materials of III-V compounds, including N-based materials, are practically used as photoconductive materials. What can be used has not been obtained so far.

Hitherto, non-single-crystal III-V compounds have been obtained by setting the production temperature to a temperature lower than that for producing crystals (600-1000 ° C.). In particular,
The group III-V compound crystal film is formed by vapor deposition or sputtering of a group III-V crystal, or by a reaction between an atomized group III metal and a molecule containing a group V element or an active molecule.
[H. Reuter, H. Schmitt, M. Boffgen, Thin Solid Films, 254
(1995) 94] Alternatively, it is manufactured on a heated substrate by a so-called organometallic CVD (MOCVD) method using an organometallic compound containing a group III metal and a compound containing a group V element. In these methods, the group III-V compound of the crystal is used to adjust the substrate temperature in the case of producing the crystal (600-
(1000 ° C).

[0008] However, the method in which a crystal is used as a raw material and which is produced by sputtering has many defects in the film and poor photoconductivity, and the MOCVD method requires low-temperature film formation in order to be amorphous. There is a problem that carbon from the organic metal remains in the film or there are many defect levels in the film, and a non-single-crystal III-V compound semiconductor that can function as a photoconductive material has not been obtained. [H.Reuter, H.Schmitt, M.Boffge
n, Thin Solid Films 254, 94 (1995)].

[0009] On the other hand, it is known that amorphous amorphous silicon is hydrogenated to reduce the density of defect states between bands, thereby enabling valence electron control. Furthermore, many studies have been made on the role of hydrogen on defects in III-V compound semiconductors in crystals. (1) Improvement of crystal dislocation defects [Y. Okada, S. Ohta, H. Shimomura, A. Kawa
bataand M. Kawabe, JJAppl. Phys., 32, L1556 (1993)],
(2) Improvement of interface defects with the surface oxide film [Y.
g, W.Widdra, SIYi, J.Merz, WEWeinBerg and E Hu, JV
ac.Sci.Tech.B12.2605 (1994)], (3) Improvement of n + -p junction surface [S.Min, WCChoi, HYCho, M. Yamaguchi, Ap
pl.Phys. Lett 64,1280 (1994)], (4) Improvement of defects due to lattice mismatch [B. Chatterjee, SARingel, R. Sie
g, R. Hoffman and I. Weinberg, Appl. Phys. Lett 65, 58 (19
94)] and (5) Passivation of bonding defects. From the fact that hydrogen has solved the problem of the role of hydrogen on the defects of III-V compound semiconductors in these crystals and the increase in the density of defect states between bands when crystalline silicon is changed to amorphous silicon,
The effect of hydrogenation can also be expected in amorphous III-V compound semiconductors.

[0010] With respect to the amorphous group III-V compound semiconductor containing hydrogen, hydrogenation hydrogen with reactive evaporation method with H ₂ a-
The photoconductivity of GaP was reported [M. Onuki, T. Fujii and H. Kub
ota, J. non-Cryst, Solids, 114, 792 (1989)], and the photoconductivity of hydrogenated a-GaAs has also been reported [V. Coscia, R. Murr.
i, N.Pinto, L.Trojani, J.Non.Cryst.Solid, 194 (1996) 10
3] However, in these semiconductors, the light-dark resistance ratio is as small as about two orders of magnitude, and the p.
There was a problem that n control could not be performed. Non-single-crystal III-V compound semiconductors made of an amorphous material or a microcrystalline material, which are passivated with hydrogen, may be made of III.
CV using organometallic compound as group material
Although the GaN of the microcrystalline film containing hydrogen was obtained by the D method, it did not show photoconductivity and was insulative [J. Knights a
nd RALujan, J. Appl. Phys., 42 (1978) 1291]. Hydrogenated amorphous GaAs produced by the plasma CVD method has only a small photoconductivity of about 10% and is far from practical use [Y. Segui, F. Carrere and A. Bui, Thin So
lid Films, 92 (1982) 303.]. In addition, the introduction of hydrogen can be expected to passivate dangling bonds caused by the non-single crystallization due to the bonding between group III atoms and group V atoms in the film. When the content is large, there is a problem that the obtained film reacts sensitively to air, and an oxidation reaction easily occurs.

[0011]

A first object of the present invention is to improve the disadvantages of such amorphous or microcrystalline non-single-crystal group III-V compound semiconductors and to improve the role of hydrogen in amorphous semiconductors. Taking advantage of its excellent photoconductive properties, high-speed response, environmental resistance and high temperature resistance with little change over time, optically active, and amorphous, suitable as a low-cost new optoelectronic material It is to provide an optical semiconductor. A second object of the present invention is to provide a semiconductor light receiving element capable of performing high-efficiency photoelectric conversion in the entire range from the ultraviolet region to the visible region. A third object of the present invention is to provide a new optoelectronic material having a large area and a low cost, which can freely select a wide range of optical gaps, has excellent photoconductive properties, high-speed response, environmental resistance and high temperature resistance. It is an object of the present invention to provide a semiconductor device using a novel amorphous or microcrystalline non-single-crystal optical semiconductor. A fourth object of the present invention is to provide a method for manufacturing a non-single-crystal optical semiconductor which can safely produce an amorphous or microcrystalline non-single-crystal optical semiconductor having the above characteristics and can be manufactured at low cost. Is to provide.

[0012]

Means for Solving the Problems The present inventors have focused on the technique of hydrogenation of an amorphous silicon semiconductor, and have studied the improvement of the defect of a conventional amorphous or microcrystalline III-V compound semiconductor as an optoelectronic material. As a result of intensive studies, it has been found that these defects can be improved by controlling the bonding state between the element contained in the film and hydrogen in the nitrogen-based III-V compound semiconductor, and the present invention has been completed. That is, the non-single-crystal optical semiconductor of the present invention is:
A non-single-crystal optical semiconductor containing at least hydrogen, a Group III element in the periodic table, and nitrogen, wherein an infrared absorption spectrum of the non-single-crystal optical semiconductor has an absorption peak (NH) indicating a bond between nitrogen and hydrogen. The ratio of the absorbance I _NH / I _CH to the absorption peak (CH) indicating the bond between carbon and hydrogen is 3 or more, and the absorption peak (NH) indicating the bond between nitrogen and hydrogen
And the absorption peak (III
-H) and the ratio I _NH / I _III-H absorbance is not less than 0.05, and an absorption peak indicating the binding of a group III element and nitrogen (III -N), the III group element and hydrogen and the absorption peak indicating the bond (III -H), the ratio I _{III- N} / I _III-H absorbance
1.5 or more, the absorption peak (III-N) is a single absorption band, and the half width of the absorption peak (III-N) is 25
0 cm ^-1 or less.

The strength ratio and the like are changed by changing the raw material of the non-single-crystal material and the manufacturing method, and are adjusted to fall within the above ranges, whereby the ratio of the group III element and the ratio of nitrogen to hydrogen can be suitably maintained. , While showing a good bonding state, the amount of carbon present in the material constituting the non-single crystal material is small, more preferably, below the detection limit,
The composition ratio of each element in the non-single crystal material becomes a suitable state,
The obtained non-single-crystal material shows stable and high performance.

Further, in the non-single-crystal optical semiconductor of the present invention, it is preferable that hydrogen is contained in a range of 0.5 atomic% to 50 atomic%, and the group III element in the periodic table is the total number of atoms. The ratio of x to the number y of nitrogen atoms is
It is between 1.0: 0.5 and 1.0: 2.0, and is preferably at least one selected from the group consisting of Al, Ga, and In. Furthermore, at least one selected from the group consisting of C, Si, Ge, Sn
It is preferable to include one or more elements and / or at least one element selected from the group consisting of Be, Mg, Ca, Zn, and Sr.

The non-single-crystal optical semiconductor of the present invention reacts an active species that has activated a compound containing nitrogen with an organometallic compound containing a Group III element in the periodic table in an atmosphere containing activated hydrogen. It can be manufactured by doing.
Activated hydrogen may be supplied by activating a compound containing hydrogen, and high-frequency discharge and / or microwave discharge may be used as the activating means. Further, it is preferable to introduce at least one or more of the organometallic compounds containing a group III element in the periodic table from the downstream side of the activating means.

According to such a method, even at a low temperature at which an amorphous film or a microcrystalline film can be grown, the organic groups are separated from the organic metal as stable molecules, are not taken into the film, and unbonded bonds are formed during film growth. Active hydrogen generated from organic groups or separately added hydrogen and active hydrogen due to hydrogen compounds acts to remove carbon on the film surface during film growth, reducing impurities to a very small amount. it can.

The non-single-crystal optical semiconductor of the present invention can be applied to a charge generation layer, a charge transport layer, and a surface layer in an electrophotographic photosensitive member. Further, the present invention can be applied to a photovoltaic element and a light receiving element.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The non-single-crystal optical semiconductor of the present invention (hereinafter, sometimes referred to as a non-single-crystal material) contains at least hydrogen, a group III element in the periodic table, and nitrogen.

The non-single crystal means that it is amorphous or microcrystalline, and may be any of an amorphous phase, a microcrystalline phase, and a mixed state of a microcrystalline phase and an amorphous phase. The crystal system of the microcrystal may be any one of a cubic system and a hexagonal system, or a state in which a plurality of crystal systems are mixed. Note that the size of the microcrystal is 5 nm to 5 μm,
It can be measured by X-ray diffraction, electron beam diffraction, shape measurement using an electron micrograph of a cross section, or the like. Here, the term “amorphous” refers to, for example, a halo pattern in which there is no ring-like diffraction pattern in the transmission electron beam diffraction pattern and the halo pattern completely lacks long-range order. , And those in which luminescent spots are seen. In such a film, almost no peak is often obtained in X-ray diffraction measurement for observing a wider range than transmission electron beam diffraction. The microcrystal refers to, for example, a transmission electron beam diffraction pattern in which a large number of bright spots are observed together with a ring-shaped diffraction pattern, or a microcrystal in which only spot-shaped bright spots are observed. In a film composed of microcrystals, in X-ray diffraction measurement, a peak slightly corresponding to a crystal plane is obtained. However, in the case of a polycrystalline film, the peak intensity is weaker than that of a single crystal, and the peak width is single crystal. Often larger than. By using such an amorphous or microcrystalline material, it is possible to form a film on a free substrate material at a low temperature, and it is a low-cost, unlimited shape and size, high-performance optoelectronic device. Can be produced.

The hydrogen concentration in the non-single-crystal material of the present invention is 0.1%.
It is preferably in the range of 5 at% to 50 at%. In order to realize an amorphous structure while maintaining a three-dimensional structure, dangling bonds are generated in both the group III element and nitrogen. Further, in order to realize a three-dimensional structure using microcrystals, dangling bonds are generated in both the group III element and nitrogen at the grain boundaries. In order to compensate for this dangling bond, a one-coordinate atom such as hydrogen or halogen can be used. In the present invention, in order to compensate for such dangling bonds, the hydrogen is bonded to the group III element and the nitrogen together. If the non-single-crystal material contains less than 0.5 atomic% of hydrogen, bond defects at grain boundaries, bond defects inside the amorphous phase, and dangling bonds are eliminated by bonding with hydrogen,
Insufficient to inactivate the defect levels formed in the band, and as a result of maintaining coupling defects and structural defects, the dark resistance is reduced and the photosensitivity is lost. Cannot work. On the other hand, if the amount of hydrogen contained in the non-single-crystal material exceeds 50 atomic%, the probability of hydrogen bonding to two or more group III elements and nitrogen increases, and these elements do not maintain a three-dimensional structure and are not two-dimensional. A chain-like network is formed, and a large number of voids are generated, especially at the crystal grain boundaries.As a result, new levels are formed in the band, and electrical characteristics are deteriorated and mechanical properties such as hardness are reduced. Property deteriorates. In addition, the film is easily oxidized,
As a result, a large amount of impurity defects are generated in the film, and good photoelectric properties cannot be obtained. Further, when the hydrogen contained in the non-single-crystal material exceeds 50 atomic%, the dopant to be doped for controlling the electrical characteristics becomes inactivated by hydrogen, and as a result, the electrically active non-crystalline material becomes inactive. A non-single-crystal optical semiconductor made of crystalline or microcrystalline cannot be obtained. The absolute value of the amount of hydrogen can be measured by hydrogen forward scattering (HFS). It can also be estimated by measuring the amount of hydrogen released by heating or measuring the infrared absorption spectrum.

The group III element in the periodic table in the non-single-crystal material of the present invention is defined as the revised version of IUPAC inorganic chemical nomenclature (1).
989) Periodic table in the old classification before the publication of III
Among the elements belonging to the group, such as B, Al, Ga, In, and Tl, among them, Al, Ga, and In are particularly preferable in terms of semiconductor performance as a nitride, such as conductivity and an optical gap. The group III element in the non-single-crystal material of the present invention has a ratio of x to y, where x is the total number of group III elements and y is the number of nitrogen atoms.
It is preferably between 1.0: 0.5 and 1.0: 2.0. If the ratio of x to y is out of this range, the number of cubic or zincblende-type parts in the bond between the group III element and nitrogen decreases, resulting in more defects. It will not function as a good semiconductor. The composition of each element in the non-single-crystal material is determined by X-ray photoelectron spectroscopy (XPS), electron microprobe, Rutherford back scattering (R
BS), a secondary ion mass spectrometer or the like.

The optical gap of the film can be arbitrarily changed depending on the mixing ratio of the group III element. Based on the optical gap of the GaN: H film, 3.2-3.5 eV, it can be increased to about 6.5 eV by adding Al.
Can handle the ultraviolet region, 1.9 eV by adding In
It can be changed to the extent, and can correspond to the visible region.

Hydrogen and III in the non-single-crystal material of the present invention
The bonding state of each of group elements, hydrogen and nitrogen, and nitrogen and group III elements can be easily measured by an infrared absorption spectrum. That is, the chemical bond state in the film is mainly II
It can be specified by the bonding state of the group I element, nitrogen and hydrogen, and their quantity relation. Furthermore, the film structure and further the characteristics of the film can be defined by grasping the relationship with carbon as an impurity in a complex manner.

The non-single crystal material of the present invention must have an absorption peak in an infrared absorption spectrum satisfying the following four requirements. (1) Absorbance ratio I _NH / I _{CH of} absorption peak (NH) indicating a bond between nitrogen and hydrogen and absorption peak (CH) indicating a bond between carbon and hydrogen is 3 or more. Absorption peak (NH) indicating the bond with hydrogen, II
Absorbance ratio I _NH / I _{III-H of} absorption peak (III-H) indicating the bond between group I element and hydrogen is 0.05 or more. (3) Absorption peak indicating the bond between group III element and nitrogen (III)
-N) and the absorbance ratio I _III-N / I _{III-H of the} absorption peak (III-H) indicating the bond between the group III element and hydrogen is 1.5.
(4) Absorption peak (III-N) is almost a single absorption band, and half width of absorption peak (III-N) is 250 cm ^-1 or less.

The relationship between the absorbances of the absorption peaks in these infrared absorption spectra will be described with reference to specific examples. FIG.
FIG. 2 is a spectrum diagram showing an infrared absorption spectrum (hereinafter, sometimes referred to as an IR spectrum) of the film produced in Example 1. Here, since gallium is used as the group III element, according to this spectrum, the absorption peak due to stretching vibration of NH 2 near 3230 cm ⁻¹ and the absorption peak near 2100 cm ⁻¹
There is an absorption peak due to stretching vibration of Ga-H. 2950cm more
There is an absorption peak due to stretching vibration of CH 2 near ^-1 . Further, there is an absorption peak due to the skeleton vibration of Ga-N near 550 cm ⁻¹ .

In this case, the ratio of the absorbance I _NH / I of the absorption peak (NH) indicating the bond between nitrogen and hydrogen to the absorption peak (III-H) indicating the bond between the group III element and hydrogen is used.
_III-H can be expressed as the ratio of the absorption intensity of the absorption peak in the vicinity of 3230cm ^-1 and near 2100 cm ^-1, in the present invention, this value must be 0.05 or more. I _NH / I _III-H
When is less than 0.05, compensation of dangling bonds is not performed with nitrogen atoms, and defects increase. In addition, the ratio of the absorbance I _NH / I _CH between the absorption peak (NH) indicating the bond between nitrogen and hydrogen and the absorption peak (CH) indicating the bond between carbon and hydrogen is 32
Can be expressed as the ratio of the absorption intensity of the absorption peak of 30 cm ^-1 and 2950 cm ^-1, in the present invention, this value must be 3 or more. When I _NH / I _CH is less than 3, the film contains a large amount of carbon, which inhibits the formation of a network between a group III element and nitrogen. Also, the ratio of the absorbance I _III-N / I between the absorption peak (III-N) indicating the bond between the group III element and nitrogen and the absorption peak (III-H) indicating the bond between the group III element and hydrogen. _III-H can be expressed as the ratio of the absorption intensity of the absorption peak of 550 cm ^-1 and 2100 cm ^-1, in the present invention, this value must be 1.5 or more. I _III-N /
When I _III-H is less than 1.5, bonds between group III atoms and nitrogen and hydrogen increase, and bonds between group III elements and nitrogen decrease.

Further, in the present invention, the absorption peak (III-N) of Ga-N near 550 cm ^-1 must be a single absorption band and the half width at 250 cm ^-1 or less. . From the result of measuring near 550 cm ^-1 in the infrared absorption spectrum using Si as the substrate, the vibration absorption peak of the bond between the group III atom and the N atom becomes single as the amorphous structure approaches the microcrystalline structure. To give a sharp shape. When compared with the phase state determined from the electron diffraction pattern, specifically, in the range where the half width exceeds 250 cm ⁻¹ , the film is an organic amorphous film, and when the half width is less than 250 cm ⁻¹ , When the half-value width is 200 cm ^-1 or less, the amorphous structure is mainly contained, but the microcrystals begin to mix. When the half-value width is 100 cm ^-1 or less, the microcrystals are mainly contained. In the present invention, the more microcrystals are contained, the better the photoconductive properties and the high-speed response are. Therefore, the half width of the absorption peak (III-N) of Ga-N is preferably 150 cm ^-1.
The following is preferred. On the other hand, the absorption band at this absorption peak position is, for example, spread to 300 cm ^-1 or more due to a plurality of absorption bands in an organic film containing a large amount of CH bonds and the like. Not suitable for purpose.

Therefore, when a non-single-crystal material satisfying the above requirements is left in the air for a long time, the infrared absorption spectrum does not change, cracks and poor adhesion do not occur, and the surface hardness is low. An excellent non-single-crystal optical semiconductor material having high electric and optical properties is obtained.

The absorption wavelength peak in the infrared absorption spectrum is 10 when the wavelength is amorphous or microcrystalline.
Shifts to higher wave numbers in the range of -40 cm ^-1 , but the same relationship applies. Further, in the present invention, the half-value width includes the case of an absorption band composed of a plurality of peaks at an absorption position mainly composed of a bond between a group III atom and nitrogen, and includes the maximum intensity of the peak and the intensity excluding the background. It is the width at the position where is halved. Alternatively, when the low wave number side cannot be completely measured, the half value width of one half of the high wave number side is doubled.

The same relationship can be applied to the infrared absorption spectrum of a film containing indium, aluminum, etc. in addition to gallium as a group III element.
As described above, when a plurality of group III elements are used, the absorption peak (III-H) indicating the bond between the group III element and hydrogen is the absorption peak indicating the bond between each element and hydrogen (for example, Ga-H, In- H,
(Each peak in the Al-H bond). For example, when In is added, 10-50 cm ^-1 on the low wavenumber side
Shift but apply a similar relationship. Absorption peaks due to other bonds also shift depending on the state and the contained elements, but the absorption peak intensity relation is handled in the same manner.

In the non-single-crystal material of the present invention, oxygen and carbon are
It is desirable that the total amount be 15 atomic% or less. When oxygen is contained in the material, this oxygen atom becomes the group III element Al, Ga, In
To form a stable bond with Al, Ga, In, and nitrogen atoms to partially form a two-dimensional flexible structure. In this case, it is difficult to take an electrically active coupling arrangement, and as a result, pn control cannot be performed. On the other hand, when carbon is contained in the material, the bond between carbon and hydrogen is more stable than the bond between Al, Ga, In and hydrogen as Group III atoms, and more hydrogen is bonded to carbon. Carbon is -CH _2- , -C
The generation of likely chain structure and voids take of H ₃ bond can not pn control for structural flexibility when the dopant was doped with defect level increases overall material. Further, in the case of a wide-gap material, the material is colored to change from yellow to brown, so that the optical characteristics are also deteriorated.

The non-single-crystal material of the present invention can be doped with another element for controlling pn. Elements for n-type include Li of the Ia group, Cu, Ag, Au, and II of the Ib group.
Mg of group a, Zn of group IIb, Si, Ge, Sn, Pb of group IVa, S, Se, Te of group IVb can be used. The p-type elements include Li, Na, K of the Ia group, Cu, Ag, Au of the Ib group, and Be, M of the IIa group.
g, Ca, Sr, Ba, Ra, Zn, Cd, Hg of IIb group, C, Si, Ge, IVb group
Sn, Pb, VIb group S, Se, Te, VIa group Cr, Mo, W, VIII group Fe, Co, Ni and the like can be used. The classification of each family is based on the old classification before the IUPAC revised edition of inorganic chemical nomenclature (1989) was published.

The dopant is preferably one that does not inhibit the binding of activated hydrogen to the group III element and nitrogen, that is, the passivation of the defect level by the activated hydrogen. In other words, it is necessary that the activated hydrogen selectively binds to the group III element and nitrogen and binds to the dopant so that it is not inactivated. From this point, Si, Ge, and Sn are particularly preferable as the n-type element, and Be, Mg, Ca, Zn, and Sr are particularly preferable as the p-type element.

When the non-single-crystal optical semiconductor of the present invention is used
At least the non-single-crystal optical semiconductor is provided on the substrate.
I just need. That is, the non-single-crystal optical semiconductor of the present invention is:
At least one element of Al, Ga, In and nitrogen and hydrogen
Comprising an n-type or p-type non-single-crystal optical semiconductor
Or a film p with a higher concentration of doping. ⁺
Or n⁺Layers may be inserted or low concentration of dopin
Membrane p⁼Or n^-Layers may be inserted. Sa
Furthermore, these p-type, i-type,
The n-type layers are different Al_xGa_yIn_z(x = 0-1.0, y = 0-1.0, z
= 0-1.0) can be expressed as Al, Ga, In and N.
The p-type, i-type, and n-type films each have a plurality of Al_xGa_y
In_zN: H (x = 0-1.0, y = 0-1.0, z = 0-1.0)
You may.

The thickness of the film made of the non-single-crystal optical semiconductor of the present invention varies depending on the application, but is preferably 0.01 to 10 μm in the case of a photovoltaic element or a light receiving element. In this case, 1 to 50 μm is preferable.

The substrate used in the present invention may be conductive or insulating, and may be crystalline or amorphous. As the conductive substrate, metals such as aluminum, stainless steel, nickel, chromium and alloy crystals thereof, Si, GaAs,
Semiconductors such as GaP, GaN, SiC, and ZnO can be given.
Alternatively, an insulating substrate having a substrate surface subjected to a conductive treatment can be used. Examples of the insulating substrate include a polymer film, glass, quartz, and ceramic. The conductive treatment is performed by forming a film of the above metal, gold, silver, copper, or the like by an evaporation method, a sputtering method, an ion plating method, or the like.

In the present invention, when a transparent conductive substrate for light incidence is used, it is preferable to use a translucent support. The translucent support, glass, quartz, sapphire, MgO, LiF, transparent inorganic materials such as CaF ₂ also, fluororesin, polyester, polycarbonate, polyethylene, polyethylene terephthalate, a transparent organic resin such as an epoxy film Alternatively, a plate, an optical fiber, a selfoc optical plate, or the like can be used.

Further, as the translucent electrode provided on the translucent support, ITO, zinc oxide, tin oxide, lead oxide,
Using a transparent conductive material such as indium oxide and copper iodide,
A material formed by a method such as evaporation, ion plating, or sputtering, or a material formed by thinning a metal such as Al, Ni, or Au to a translucent level by evaporation or sputtering is used. Further, these translucent electrodes may be provided directly on the optical semiconductor layer.

Next, a method for manufacturing a non-single-crystal optical semiconductor according to the present invention will be described. The non-single-crystal optical semiconductor of the present invention reacts an active species that has activated a compound containing nitrogen with an organometallic compound containing a Group III element in the periodic table in an atmosphere containing activated hydrogen. It can be manufactured by forming a layer on a substrate. The above manufacturing method
It is characterized in that an organometallic compound is used as a raw material for a Group III element in the periodic table and that the reaction is performed at a low temperature in the presence of activated nitrogen and hydrogen.

The activation of the nitrogen-containing compound of the present invention means
Bringing the compound containing nitrogen into the energy state required for reaction with the organometallic compound containing a group III element, or
It means that a compound containing nitrogen is decomposed into excited species. In addition, activated hydrogen can be obtained by activating an excited hydrogen gas or by activating a compound containing hydrogen. Compounds containing hydrogen include H ₂ , hydrocarbons,
Hydrogen halide and an organometallic compound are mentioned, and H ₂ is preferable because impurities are not mixed. The activated hydrogen and activated nitrogen formed by the discharge energy may be controlled independently, or may be activated simultaneously using a gas containing both nitrogen and hydrogen atoms, such as NH ₃ . In this case, H ₂ may be further added. Further, a condition under which active hydrogen is liberated from the organometallic compound may be used. In this way, the activated II
Group I atoms and nitrogen atoms are present in a controlled state, and even if the hydrogen atom makes the methyl or ethyl group an inert molecule such as methane or ethane, despite the low temperature, almost no carbon enters, An extremely small amount of an amorphous or microcrystalline film with suppressed film defects can be formed.

As the activating means, a high-frequency discharge, a microwave discharge, an electrocyclotron resonance method, a helicon plasma method, or the like can be used. These activation means may be used alone or in combination of two or more. Further, high frequency discharges, microwave discharges, or electron cyclotron resonance methods may be used in combination. In the case of high-frequency discharge, it may be an induction type or a capacitance type. When different activating means (exciting means) are used, it is necessary to enable simultaneous discharge at the same pressure, and a pressure difference may be provided between the inside of the discharge tube and the film forming unit. When the same pressure is used, when different activating means (exciting means), for example, a microwave and a high-frequency discharge are used, the excitation energy of the excited species can be largely changed, which is effective for controlling the film quality.

The organometallic compound containing a Group III element in the periodic table of the present invention includes trimethylaluminum,
Liquid or solid such as triethyl aluminum, tertiary butyl aluminum, trimethyl gallium, triethyl gallium, tertiary butyl gallium, trimethyl indium, triethyl indium, tertiary butyl indium, etc. are vaporized and mixed alone or by bubbling with a carrier gas Can be used with

The nitrogen-containing compound of the present invention includes N
_{2, NH 3, NF 3,} N 2 H 4, a gas such as methylhydrazine,
Liquid nitrogen compounds can be used.

In the non-single-crystal optical semiconductor of the present invention, there are many cases where the raw material or the auxiliary raw material does not contain hydrogen in the reactive evaporation method, ion plating, reactive sputtering and the like. It can be obtained by performing film formation in an atmosphere of hydrogen that has been performed.

Hereinafter, the method for producing a non-single-crystal material of the present invention will be specifically described together with the production apparatus used. FIG. 3 is a schematic view of an apparatus used for the plasma activated MOCVD method. The plasma-activated MOCVD method is a method for producing a thin film using plasma as an activating means. In FIG.
1 is a container which can be evacuated to a vacuum, 2 is an exhaust port, 3 is a substrate holder, 4 is a heater for heating the substrate, and 5 and 6 are quartz tubes connected to the container 1. Communicating. Further, a gas introduction tube 11 is connected to the quartz tube 5, and a gas introduction tube 12 is connected to the quartz tube 6.

In this apparatus, for example, N ₂ is used as a nitrogen source and introduced into the quartz tube 5 from the gas introduction tube 9.
A microwave of 2.45 GHz is supplied to a microwave waveguide 8 connected to a microwave oscillator (not shown) using a magnetron to generate a discharge in the quartz tube 5. This gives N
₂ is activated and the active species is introduced into the container 1. From another gas inlet 10, for example, H ₂ is introduced into the quartz tube 6 as a hydrogen element source. A high frequency of 13.56 MHz is supplied from a high frequency oscillator (not shown) to the high frequency coil 7 to generate a discharge in the quartz tube 6. Thereby, H ₂ is activated, and the active species is introduced into the container 1. By introducing trimethylgallium from the gas introduction pipe 12 from the downstream side of the discharge space, the activated species that activated nitrogen, the activated species that activated hydrogen, and trimethylgallium reacted, and hydrogen was deposited on the substrate. An amorphous or microcrystalline non-single-crystal gallium nitride optical semiconductor can be formed.

Whether the non-single-crystal material of the present invention becomes amorphous or microcrystalline depends on conditions such as the type of substrate, substrate temperature, gas flow rate and pressure, and discharge output. Further, the composition of the non-single-crystal material that determines the value of the optical gap depends on the concentrations and flow rates of the source gas and the carrier gas. The film thickness is
It depends not only on the concentration and flow rate of the source gas and the carrier gas, but also on the energy of the discharge. However, regarding the control of the film thickness,
It is preferable to control the film formation time.

In the case of a crystalline substrate or a crystalline substrate whose surface has been subjected to an etching treatment, the substrate is likely to become microcrystalline. For example, a Si substrate or the like can be suitably used. In addition, the substrate temperature is set to 100 ° C. for non-single crystal.
To 600 ° C. is preferable, and when the substrate temperature is higher than 300 ° C., microcrystals are easily formed, which is preferable.

Various raw material gases are introduced through gas inlets, and hydrocarbons such as hydrogen, N ₂ , methane and ethane, and halogenated carbons such as CF ₄ and C ₂ F ₆ are used as carrier gases. be able to. The substantial flow rate of the source gas is preferably 0.001 to 10 sccm from the viewpoint of film quality and the like. When the flow rate of the group III source gas is small, microcrystals are easily formed, which is preferable. However, the influence of the substrate temperature on the substrate temperature and the flow rate of the group III raw material gas is more significant. When the substrate temperature is higher than 300 ° C., even when the flow rate of the group III raw material gas is large, microcrystals are easily formed. On the other hand, when the flow rate of the group III source gas is large and the discharge output is insufficient, an organic film tends to be formed, which is not preferable.

In particular, the organometallic compound containing a group III element is preferably placed downstream of the discharge space (in FIG. 3, the gas introduction pipe 11 or the gas introduction pipe 12) in order to avoid film formation in the discharge space.
It is preferable to introduce the gas through the gas introduction pipe provided in the above. Also,
When introducing an organometallic compound containing several Group III elements, they may be introduced from the same gas introduction tube or from different gas introduction tubes.

Further, a gas containing at least one element selected from C, Si, Ge, and Sn, or a gas containing at least one element selected from Be, Mg, Ca, Zn, and Sr is used. By introduction, an amorphous or microcrystalline nitride semiconductor of any conductivity type such as n-type and p-type can be obtained. C
In this case, carbon of an organometallic compound may be used depending on the conditions. These are preferably introduced from a gas introduction pipe provided on the downstream side of the discharge space, like the organometallic compound containing a group III element.

As the element sources of C, Si, Ge, and Sn, SiH ₄ , Si ₂
Compounds such as H ₆ , GeH ₄ , GeF ₄ , SnH ₄ are converted to Be, Mg, Ca, Zn,
Elemental sources of Sr include BeH ₂ , BeCl ₂ , BeCl ₄ , biscyclopentadienyl magnesium, dimethyl calcium,
Compounds such as dimethylstrontium, dimethylzinc and diethylzinc can be used in a gaseous state. As a doping method, a known method such as a thermal diffusion method or an ion implantation method can be employed.

When the discharge output is high, microcrystals are apt to be formed. For example, when film formation is performed by using active hydrogen in combination with hydrogen discharge, microcrystallization is performed more than when no film is formed. Is preferred.

In order to obtain an optical semiconductor device using a non-single-crystal optical semiconductor made of an amorphous or microcrystalline semiconductor according to the present invention, an optical semiconductor is formed on a conductive or conductively treated substrate by the method described above. By setting the film thickness to 1 μm to 10 μm, an electrophotographic photosensitive member can be obtained. The optical semiconductor may be used as a charge generation layer, and a charge transport layer mainly composed of an organic compound may be formed thereon. Further, since the optical semiconductor can arbitrarily set transmitted light, it can be used as a charge transport layer on an inorganic or organic charge generation layer. Further, the charge transport layer may be provided as a lower layer. Further, a surface protective layer provided on the surface and having the function of a charge transport layer can also be provided.

A photovoltaic element can also be formed by forming an optical semiconductor on a substrate obtained by conducting or conducting a non-single-crystal optical semiconductor made of an amorphous or microcrystalline semiconductor of the present invention by the above-described method. Most simply, a photoelectromotive force can be generated at the Schottky barrier using a transparent conductive film of ITO or zinc oxide or a thin metal film as an electrode on this optical semiconductor. Furthermore, a photovoltaic element can be obtained by laminating p-type and n-type layers or p-type, i-type and n-type layers. The non-single-crystal optical semiconductor comprising an amorphous or microcrystalline semiconductor of the present invention can change the optical gap arbitrarily, and may have a tandem-type multilayer structure in accordance with the absorption wavelength as an active region for photocarrier generation. Therefore, a highly efficient solar cell can be manufactured. In the case of a tandem type, the layers are stacked on a conductive substrate so that the optical gap is gradually increased. On top of this, a transparent insulating layer is provided. In addition, an optical gap is formed on a transparent conductive substrate so that the optical gap is gradually reduced, and the conductive layer is formed as an electrode.

The photo-semiconductor can also be formed as a light-receiving element by forming the photo-semiconductor on the substrate obtained by conducting or treating the non-single-crystal optical semiconductor made of the amorphous or microcrystalline semiconductor of the present invention. In this case, a single layer may be used, or a tandem-type multilayer structure in which the optical gap is gradually increased toward the light incident side may be used. In addition, a wavelength-separated light-receiving element can be obtained by extracting photocurrents independently from layers having different optical gaps. In this case, an intermediate transparent conductive electrode or an intermediate conductive electrode that transmits the sensitivity wavelength of the lower optical semiconductor is provided so that light can pass through a plurality of optical semiconductor electrodes other than the lowermost layer. Further, the purpose of suppressing current injection at the time of darkness between the transparent conductive electrode and the optical semiconductor or / and between the intermediate electrode and the optical semiconductor and / or between the conductive substrate and the optical semiconductor to widen the dynamic range and improve the response speed. An intermediate layer may be provided for the purpose. The intermediate _{layer, AlN, Al x Ga (1} -x) N, Al x Ga y In z N
Etc. can be used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Using the manufacturing apparatus shown in FIG. 2, a cleaned Al substrate, a quartz substrate, and a Si wafer were placed on a substrate holder 3, and the inside of the container 1 was evacuated through an exhaust port 2. 25
Heated to 0 ° C. Nitrogen gas is 25mm in diameter from the gas inlet tube 9.
1000 sccm was introduced into the quartz tube 5, and a microwave of 2.45 GHz was set to 250 W output through the micro waveguide 8, matching was performed with a tuner, and a first plasma discharge was performed. The reflected wave at this time was 0W. Hydrogen gas was introduced from the gas introduction tube 10 into the quartz tube 6 having a diameter of 30 mm at 200 sccm. 2.
The microwave output of 45 GHz was set to 100 W and a second plasma discharge was performed. The reflected wave was 0W. In this state, trimethylgallium (TMGa) vapor kept at 0 ° C. from the gas introduction pipe 11 is passed through a mass flow controller while bubbling using hydrogen as a carrier gas.
sccm was introduced. At this time, the reaction pressure measured with a Baratron vacuum gauge was 66.5 Pa. Film formation is performed for 30 minutes, and 0.5 μm Ga
An N: H film was prepared.

When the composition of the film formed on the Si substrate simultaneously with the a-GaN: H film was measured by RBS (Rutherford Back Scattering), the Ga / N ratio was 0.95, which was almost stoichiometric. Had become. In addition, hydrogen was 22 atomic% by HFS measurement. By IR spectrum measurement, it was confirmed that these hydrogens were contained in the GaN film as Ga-H, NH. FIG. 1 shows the IR spectrum of the prepared film. As can be seen from Figure 1, each Ga-H, the absorption peak due to the binding of Ga-N is 2099Cm ^-1 and 554cm ^-1, NH
The intensity ratio of the absorbance of CH and CH, the intensity ratio of the absorbance of NH and Ga-H, and the intensity ratio of the absorbance of Ga-N and Ga-H are 9
And 0.38 and 2.86, respectively. In addition, the half width of the Ga—N absorption peak was as broad as 180 cm ⁻¹ , indicating that it was amorphous. In addition, only a halo pattern could be detected in the electron diffraction spectrum, indicating that the sample was amorphous. The optical gap was 3.2 eV.

When the dark resistance was measured, it was 10 ⁺¹⁵ Ωcm. When irradiated with 325 nm light of a helium-cadmium (He-Cd) laser, the response was 0.1 s or less and the photocurrent flowed 1 μA. When off was repeated, it was found that there was a dynamic range of 3 digits or more. FIG. 3 shows the measurement results. In addition, it was found that the light quantity and the output current had a substantially linear relationship, and that the output was stable and could be used as a photodetector even in continuous irradiation. This detector did not respond under a light source containing no ultraviolet light and was able to detect ultraviolet light even in the presence of strong visible light. Furthermore, even when this film was left in the air for 12 months, no change was observed in the IR spectrum, indicating that the film was stable in the air.

Comparative Example 1 The flow rate of nitrogen gas was set to 500 sccm, and trimethylgallium was
A film was formed under the same conditions as in Example 1 except that the temperature was maintained at 0 ° C., and 3 sccm was introduced without direct bubbling, and the second plasma discharge with hydrogen gas was not performed. Perform film formation for 30 minutes,
A μm GaN: H 2 film was produced. The hydrogen concentration is 55 atomic% and I
By R spectrum measurement, it was confirmed that these hydrogens were contained in the GaN film as Ga-H, NH. FIG. 4 shows the IR spectrum of the formed film. As can be seen from FIG. 4, the absorption peak of Ga-H is 2105 cm ^-1 , and the absorption band of 571 cm ^-1 corresponding to the absorption peak of Ga-N is composed of a plurality of absorption bands, and overlaps at this resolution. In this case, as the absorption intensity and the half width, the absorption intensity and the half width including such a plurality of absorption peaks are used. The intensity ratio of the absorbance of NH and CH, the intensity ratio of the absorbance of NH and Ga-H, and the ratio of Ga-N and Ga
The intensity ratio of the absorbance of -H was 0.8, 0.19, and 2.1, respectively. In addition, the half width of the Ga-N absorption peak was 270 cm ^-1, which was broad, indicating that the film was an amorphous film. This film is 4
Leaving it in the atmosphere for 16 months
00cm with the new absorption appears in the vicinity of ^{-1 ~1700cm -1,} greatly changes the shape of the absorption band near 3000cm ^-1 ~3500cm ^-1, it was found that the film structure has changed. Further, the photoconductive properties were extremely poor, and almost no photocurrent flowed.

Comparative Example 2 A film was formed under the same conditions as in Example 1 except that microwave discharge was not performed when hydrogen gas was introduced from the gas introduction pipe 10. Film formation was performed for 30 minutes to produce a 0.5 μm GaN: H film. The hydrogen concentration was 35 atomic%, and it was confirmed by IR spectrum measurement that the hydrogen was contained in the GaN film as Ga-H, NH. FIG. 5 shows the IR spectrum of the formed film. As can be seen from FIG. 5, 571cm ^-1 absorption peak Ga-H is equivalent to the absorption peak of 2105cm ^-1, Ga-N
Are composed of a plurality of absorption bands, which overlap at this resolution. In this case, as the absorption intensity and the half width, the absorption intensity and the half width including such a plurality of absorption peaks are used. The intensity ratio of the absorbance of NH and CH, the intensity ratio of the absorbance of NH and Ga-H, and the intensity ratio of the absorbance of Ga-N and Ga-H were 2.7, 0.2, and 1.2, respectively. The half width of the Ga—N absorption peak was 210 cm ^−1, which was broad, indicating that the film was an amorphous film. The membrane new absorption appears in the vicinity of 1600cm ^-1 ~1700cm ^-1 of IR spectrum by leaving in 4 months atmosphere, it was found that the film structure has changed. The initial photoconductive properties were good, but deteriorated over time.

Example 2 Under the same substrate conditions as in Example 1, trimethylindium (TMIn) maintained at 30 ° C. was used as a carrier gas through a gas introduction pipe 12 at a pressure of 1.01 × 10 ⁵ Pa through a mass flow controller. 3 sccm was introduced. In this state, ³ sccm was introduced through a mass flow controller at a pressure of 1.01 × 10 ⁵ Pa while bubbling trimethylgallium (TMGa) vapor maintained at −10 ° C. from a gas introduction pipe 11 using hydrogen gas as a carrier gas. At this time, the reaction pressure measured with a Baratron vacuum gauge was 66.5 Pa. The film was formed for 30 minutes to produce a 0.5 μm InGaN: H 2 film.

The film fabricated under the same conditions as the a-GaInN: H film
The composition was (In + Ga) / N 2 ratio 0.65. Also, the In / Ga concentration
The ratio was 0.25. In addition, hydrogen by HFS measurement is 26 atoms
%Met. By IR spectrum measurement, these waters
Element is contained in this GaInN film as Ga-H, In-H, N-H.
I was sure that. FIG. 6 shows the IR spectrum of the prepared film.
Shown in As can be seen from FIG. 6, (Ga + In) -H, (Ga + In) -N
Absorption peak of 2077cm ^-1, 518cm^-1Absorbance of N-H and C-H at
Intensity ratio, N-H and (Ga + In) -H absorbance intensity ratio,
The intensity ratio of the absorbance of (Ga + In) -N and (Ga + In) -H is respectively
∞, 0.09 and 1.67. In addition, the Ga, In-N absorption peak
Half width is 240cm^-1Is broad and amorphous
all right. The optical gap was 2.3 eV. Xenon La
The pump light was split by a spectrometer at a center wavelength of 500 nm and irradiated.
Photocurrent flowed 160 μA, repeated on / off at high speed
But you can see that there is more than two digits of dynamic range
Was. In addition, the light amount and the output current have a substantially linear relationship,
The output is stable even during continuous irradiation and can be used as a photodetector.
I found that it can be used. In addition, this membrane is 12 months large
Even when left in the air, the IR spectrum
No change is seen and it is stable in the atmosphere
Was.

Example 3 Under the same conditions as in Example 2, trimethylindium (TMIn) was introduced into a 5 sccm reaction region using hydrogen gas as a carrier gas, and 1 sccm of trimethylgallium was used as a hydrogen gas as a carrier gas.
Introduced. At this time, the reaction pressure measured with a Baratron vacuum gauge was 66.5 Pa. After 30 minutes of deposition, 0.5 μm InGaN: H
A film was prepared.

The film fabricated under the same conditions as the a-GaInN: H film
The composition was 0.75 in terms of (In + Ga) / N 2 ratio. Also, the In / Ga concentration
The ratio was 0.6. 20 atoms of hydrogen by HFS measurement
%Met. By IR spectrum measurement, these waters
Element is contained in this GaInN film as Ga-H, In-H, N-H.
I was sure that. FIG. 7 shows the IR spectrum of the prepared film.
Shown in As can be seen from FIG. 7, (Ga + In) -H, (Ga + In) -N
Absorption peak of 2060cm ^-1, 508cm^-1Absorbance of N-H and C-H at
Intensity ratio, N-H and (Ga + In) -H absorbance intensity ratio,
The intensity ratio of the absorbance of (Ga + In) -N and (Ga + In) -H is respectively
∞, 0.12 and 1.59. In addition, the Ga, In-N absorption peak
Half width is 220cm^-1Is broad and amorphous
all right. The optical gap was 2.0 eV. Xenon La
The pump light was split by a spectroscope at a central wavelength of 600 nm and irradiated.
Photocurrent flowed 200μA, repeated on / off at high speed
But you can see that there is more than two digits of dynamic range
Was. In addition, the light amount and the output current have a substantially linear relationship,
The output is stable even during continuous irradiation and can be used as a photodetector.
I found that it can be used. In addition, this membrane is 12 months large
Even when left in the air, the IR spectrum
No change is seen and it is stable in the atmosphere
Was.

Example 4 Using the manufacturing apparatus shown in FIG. 2, a cleaned Al substrate, a quartz substrate, and a Si wafer were placed on a substrate holder 3, and the inside of the container 1 was evacuated through an exhaust port 2. 30
Heated to 0 ° C. Nitrogen gas is 25mm in diameter from the gas inlet tube 9.
1000 sccm was introduced into the quartz tube 5, and a microwave of 2.45 GHz was set to 300 W output through the micro waveguide 8, matching was performed with a tuner, and discharge was performed. The reflected wave at this time was 0 W. Hydrogen gas is 30mm in diameter from gas inlet tube 10.
1000 sccm was introduced into the quartz tube 6 of FIG. The 13.56 MHz high frequency output was set to 100 W. The reflected wave was 0W. In this state, 2 sccm of trimethylgallium (TMGa) kept at −10 ° C. was introduced from the gas introduction pipe 11 at a pressure of 1.01 × 10 ⁵ Pa through a mass flow controller using hydrogen gas as a carrier gas. At this time, the reaction pressure measured with a Baratron vacuum gauge was 66.5 Pa. Perform film formation for 60 minutes,
A 4 μm GaN: H film was produced. The composition of this GaN: H film is
Ga / N ratio was stoichiometric at 0.95. Hydrogen was 10 atomic%. By IR spectrum measurement, it was confirmed that these hydrogens were contained in the GaN film as Ga-H, NH. FIG. 8 shows an IR spectrum of the formed film.
As can be seen from FIG. 8, the peaks of NH and Ga-H are 3224 cm ^-1 .
2113cm ^-1, a peak of the Ga-N was 555cm ^-1. NH and CH
, The intensity ratio between NH and Ga-H, and the intensity ratio between Ga-N and Ga-H are ∞ and 0.9, respectively.
And 11.1. The half width of the Ga-N absorption peak is 1
It was found to be sharp and microcrystalline at 10 cm ^-1 . The electron diffraction spectrum showed that a spot pattern could be detected and the crystal was microcrystalline. Optical gap is 2.
9 eV. When dark resistance was measured, it was 10 ⁺¹⁰ Ωcm.When irradiated with a helium-cadmium (He-Cd) laser at 325 nm, the response was 0.1 s or less and the photocurrent was 100 μA.
Flow and light resistance were found to be in the order of 10 ⁺⁶ Ωcm.
When on / off was repeated at high speed, it was found that there was a dynamic range of 3 digits or more. Further, it was found that the light quantity and the output current had a substantially linear relationship, and that the output was stable and could be used as a light receiving element even in continuous irradiation. This light receiving element did not respond under a light source containing no ultraviolet light and was able to detect ultraviolet light even in the presence of strong visible light. Furthermore, even when this film was left in the air for 12 months, no change was observed in the IR spectrum, indicating that the film was stable in the air.

Example 5 Example 4 was repeated except that trimethylgallium (TMGa) was introduced at 5 sccm using hydrogen gas as a carrier without performing high-frequency discharge.
Film formation was performed under the same conditions as described above. Perform film formation for 60 minutes, 0.2 μm
A GaN: H film was produced. The composition of this GaN: H film was stoichiometric with a Ga / N ratio of 0.98. Hydrogen was 15 atomic%. By IR spectroscopy, these hydrogens were Ga
It was confirmed that -H and NH were contained in this GaN film. FIG. 10 shows the IR spectrum of the formed film. As can be seen from FIG. 10, the Ga-H peak was 2100 cm ^-1 and the Ga-N peak was 546 cm ^-1 . Intensity ratio of absorbance between NH and CH, N
The intensity ratio of the absorbance of -H and Ga-H, and the intensity ratio of the absorbance of Ga-N and Ga-H were ∞, 0.30 and 6.7, respectively. The half width of the Ga-N absorption peak was 120 cm ^-1. It was found to be sharp and microcrystalline. The electron diffraction spectrum showed that a spot pattern could be detected and the crystal was microcrystalline. The optical gap was 2.9 eV. When the dark resistance was measured, it was 10 ⁺¹⁰ Ωcm, and when irradiated with helium-cadmium (He-Cd) laser light of 325 nm, the response was 0.1 s or less, the photocurrent flowed 150 μA, and the light resistance was 10 ⁺⁵ Ω.
It turned out to be on the order of cm. When on / off was repeated at high speed, it was found that there was a dynamic range of 3 digits or more. It was also found that the light quantity and the output current had a substantially linear relationship, and that the output was stable and could be used as a light receiving element even in continuous irradiation. This light receiving element did not respond under a light source containing no ultraviolet light and was able to detect ultraviolet light even in the presence of strong visible light. In addition, this membrane
Even when left in the air for months, no change was observed in the IR spectrum, indicating that the IR spectrum was stable in the air.

Example 6 A film was formed under the same conditions as in Example 4 except that the substrate temperature was 400 ° C. and high-frequency discharge was performed at 100 W. Film formation was performed for 60 minutes to produce a 0.2 μm GaN: H 2 film. The composition of this GaN: H 2 film was 0.98 in Ga / N ratio and was stoichiometric.
Hydrogen was 5 atomic%. By IR spectrum measurement, it was confirmed that these hydrogens were contained in the GaN film as Ga-H, NH. FIG. 11 shows the IR spectrum of the formed film. As can be seen from FIG. 11, the Ga-H peak is
2128cm ^-1, a peak of the Ga-N was 558 cm ^-1. NH and C-
The intensity ratio of the absorbance of H, the intensity ratio of the absorbance of NH and Ga-H, and the intensity ratio of the absorbance of Ga-N and Ga-H are ∞ and 0.5, respectively.
And 11.4. The half width of the Ga-N absorption peak is 80 cm.
It was found to be sharp and microcrystalline at ^-1 . The electron diffraction spectrum showed that a spot pattern could be detected and the crystal was microcrystalline. The optical gap was 2.9 eV. The dark resistance was measured to be 10 ⁺⁹ Ωcm, and when irradiated with a helium-cadmium (He-Cd) laser at 325 nm, the response was 0.1 s or less, the photocurrent flowed 150 μA, and the light resistance was 10 ⁺⁵ It turned out to be on the order of Ωcm. Fast and on
When / off was repeated, it was found that there was a dynamic range of 3 digits or more. Further, it was found that the light quantity and the output current had a substantially linear relationship, and that the output was stable and could be used as a light receiving element even in continuous irradiation. This light receiving element did not respond under a light source containing no ultraviolet light and was able to detect ultraviolet light even in the presence of strong visible light. Furthermore, even when this film was left in the air for 12 months, no change was observed in the IR spectrum, indicating that the film was stable in the air.

Example 7 Using the manufacturing apparatus shown in FIG. 2, a cleaned Al substrate, a quartz substrate, and a Si wafer were placed on a substrate holder 3, and the inside of the container 1 was evacuated through an exhaust port 2. 25
Heated to 0 ° C. Nitrogen gas is 25mm in diameter from the gas inlet tube 9.
1000 sccm was introduced into the quartz tube 5, and a microwave of 2.45 GHz was set to 250 W output through the micro waveguide 8, matching was performed with a tuner, and a first plasma discharge was performed. The reflected wave at this time was 0W. Hydrogen gas was introduced from the gas introduction tube 10 into the quartz tube 6 having a diameter of 30 mm at 200 sccm. 2.
The microwave output of 45 GHz was set to 100 W and a second plasma discharge was performed. The reflected wave was 0W. In this state, trimethylgallium (TMGa) vapor held at 0 ° C. from the gas introduction pipe 12 is passed through a mass flow controller while bubbling using hydrogen as a carrier gas.
sccm was introduced. At this time, the reaction pressure measured with a Baratron vacuum gauge was 66.5 Pa. Film formation is performed for 30 minutes, and 0.2 μm Ga
An N: H film was prepared.

When the composition of the film formed on the Si substrate simultaneously with the a-GaN: H film was measured by RBS (Rutherford Back Scattering), the Ga / N ratio was 0.98 and almost the stoichiometric ratio. Had become. In addition, hydrogen was 25 atomic% by HFS measurement. By IR spectrum measurement, it was confirmed that these hydrogens were contained in the GaN film as Ga-H, NH. FIG. 12 shows the IR spectrum of the formed film. As can be seen from FIG. 12, the absorption peaks due to Ga-H and Ga-N bonds are 2100 cm ⁻¹ and 550 cm ⁻¹ , respectively, and NH
The intensity ratio of the absorbances of CH and CH, the intensity ratio of the absorbance of NH and Ga-H, and the intensity ratio of the absorbance of Ga-N and Ga-H are 11
And 0.42 and 2.5. Further, the half width of the Ga-N absorption peak was as broad as 190 cm ^-1 , indicating that it was amorphous. In addition, only a halo pattern could be detected in the electron diffraction spectrum, indicating that the sample was amorphous.

The dark resistance was measured to be 10 ⁺¹⁵ Ωcm, and when a helium-cadmium (He-Cd) laser of 325 nm was irradiated, the response was 0.1 s or less and the photocurrent flowed 1 μA. When off was repeated, it was found that there was a dynamic range of 3 digits or more. In addition, it was found that the light quantity and the output current had a substantially linear relationship, and that the output was stable and could be used as a photodetector even in continuous irradiation. This detector did not respond under a light source containing no ultraviolet light and was able to detect ultraviolet light even in the presence of strong visible light. Further, even when this film was left in the air for 12 months, no change was observed in the IR spectrum.
It was found to be stable in the atmosphere.

Example 8 The same conditions as in Example 6 were adopted except that silane gas was introduced into the quartz tube 6 having a diameter of 30 mm from the gas introduction tube 12 together with hydrogen gas at a flow rate of 1000 sccm so that the concentration became 500 ppm with respect to GaN.
A gold (Au) electrode was vacuum-deposited on the film formed on the ITO substrate, and the photoconductivity was measured. When a positive voltage and a negative voltage are applied to the ITO side after exposure with 254 nm light from a low-pressure mercury lamp where absorption on the surface is dominant, the photocurrent at the negative voltage can flow 100 times more at the negative voltage than at the positive voltage. As a result, it was shown that it was an n-type.

Example 9 Biscyclopentadienyl kept at 50 ° C. was introduced together with hydrogen gas into a quartz tube 6 having a diameter of 30 mm from a gas introduction tube 12 together with hydrogen gas.
A gold (Au) electrode was vacuum-deposited on the film formed on the ITO substrate under the same conditions as in Example 6 except that sccm was introduced and the concentration was 1000 ppm with respect to GaN, and the photoconductivity was measured. did. It can be seen that the photocurrent when exposed to 254 nm light from a low-pressure mercury lamp where absorption on the surface is dominant and a positive potential and a negative potential are applied to the ITO side flows more when the positive potential is applied than when the negative potential is applied. , P-type.

Example 10 A 5 μm a-GaN: H film was formed on an Al substrate under the same conditions as in Example 1 except that the time for film formation was extended to 5 hours, and the electrophotographic characteristics were measured. did. When charged with a −5 kV corotron and irradiated with light using a xenon-mercury (Xe-Hg) lamp, it was charged to −100 V before light irradiation, but became 0 V after light irradiation. I found it could be used.

Embodiment 11 Under the same conditions as in Embodiment 2, a 0.25 μm InGa
An N: H 2 film was prepared, and a film obtained by dispersing a 40% by weight of a trimethylamine-based charge transporting agent in polycarbonate was 10 μm thick.
It was formed by coating and drying, and the electrophotographic characteristics were measured. When charged with a -5 kV corotron while rotating, and irradiated with light using a xenon lamp, it was charged at -500 V before light irradiation, but became -20 V after light irradiation, and it can be used as an electrophotographic photosensitive member. Do you get it.

Example 12 Under the same conditions as in Example 1, a 0.25 μm InGa
An N: H film was prepared, and a 5: 1 film was formed thereon under the same conditions as in Example 10.
An a-GaN: H film having a thickness of μm was formed, and electrophotographic characteristics were measured.
When charged with a -5 kV corotron while rotating, and irradiated with 500 nm light using a xenon lamp and an interference filter, those charged to -90 V before light irradiation became -0 V after light irradiation, and It turned out that it can be used as a photoreceptor.

Example 13 A film was formed on an ITO substrate under the same conditions as in Example 4. A gold (Au) electrode was deposited on this film, and the voltage was increased from 1.0 V to −
The voltage was changed to 0.5 V, the light of a xenon-mercury (Xe-Hg) lamp was condensed by a quartz lens, irradiated from the ITO side, and the photocurrent was measured. As a result, a photocurrent of 1.5 μA flowed at 0 V. It was also found that the photocurrent was 0 A at 0.5 V and 0.5 V was obtained as a voltage, indicating that this device can be used as a photovoltaic device.

Example 14 A film was formed on an ITO substrate under the same conditions as in Example 3. A gold (Au) electrode was deposited on this film, and the voltage was increased from 1.0 V to −
The voltage was changed to 0.5 V, the light of a xenon-mercury (Xe-Hg) lamp was condensed and irradiated by a quartz lens, and the photocurrent was measured. As a result, a photocurrent of 10 μA flowed at 0 V. It was also found that the photocurrent was 0 A at 0.5 V and 0.5 V was obtained as a voltage, indicating that this device can be used as a photovoltaic device.

Example 15 Under the same conditions as in Examples 8 and 9, on an ITO substrate,
Two layers were stacked to form a 0.2 μm pn-type photovoltaic element. A gold (Au) electrode was deposited on this film, the voltage was changed from 1.0 V to -0.5 V, and the light of a xenon-mercury (Xe-Hg) lamp was condensed and irradiated with a quartz lens, and the photocurrent was As a result, a photocurrent of 15 μA flowed at 0 V. 0.8V
As a result, it was found that the photocurrent was 0 A, and a voltage of 0.8 V was obtained, indicating that this device could be used as a photovoltaic device.

From Examples 1 to 7 and Comparative Examples 1 and 2, the non-single-crystal optical semiconductor of the present invention is stable even in the air, and has excellent ultraviolet photoconductive properties, visible light conductive properties, and high-speed response. You can see that there is. Examples 4 to 6 also show that as the content of microcrystals increases, the value of dark resistance decreases and the amount of flowing photocurrent increases. Examples 8 to 15 show that the non-single-crystal optical semiconductor of the present invention can be used as an electrophotographic photosensitive member and a photovoltaic element.

[0081]

According to the present invention, the non-single-crystal optical semiconductor of the present invention comprises:
It improves the shortcomings of conventional amorphous and microcrystalline III-V compound semiconductors, has excellent photoconductive properties and high-speed response, and has excellent high-speed response and aging stability without ghost and fatigue. It has excellent characteristics that it has environmental characteristics and high temperature resistance, and can perform photoelectric conversion with high conversion efficiency in the entire range from the ultraviolet region to the visible region. In addition, the non-single-crystal optical semiconductor of the present invention has an optical gap that is variable in the entire region from red to ultraviolet, and has a wide light range from visible to ultraviolet due to high light transmittance, low dark conductivity, and high light sensitivity. Can be used effectively. In addition, by applying the non-single-crystal optical semiconductor of the present invention, light resistance,
An electrophotographic photoreceptor, a high-efficiency solar cell, a high-speed TFT, a high-performance light-receiving element, etc., which are excellent in heat resistance and oxidation resistance and can respond at high speed, can be realized. Furthermore, the non-single-crystal optical semiconductor of the present invention, which is made of an amorphous or microcrystalline semiconductor, can be manufactured safely at a low temperature, so that a high-performance device can be manufactured at low cost.

[Brief description of the drawings]

FIG. 1 is a spectrum diagram showing an IR spectrum of a film produced in Example 1.

FIG. 2 is a schematic view of an apparatus used for a plasma-activated MOCVD method.

FIG. 3 is a graph showing a change in current at the time of light irradiation on / off of a film manufactured in Example 1.

FIG. 4 is a spectrum diagram showing an IR spectrum of a film produced in Comparative Example 1.

FIG. 5 is a spectrum diagram showing an IR spectrum of a film produced in Comparative Example 2.

FIG. 6 is a spectrum diagram showing an IR spectrum of a film produced in Example 2.

FIG. 7 is a spectrum diagram showing an IR spectrum of a film produced in Example 3.

FIG. 8 is a spectrum diagram showing an IR spectrum of a film produced in Example 4.

FIG. 9 is a spectrum diagram showing an electron diffraction spectrum of a film produced in Example 4.

FIG. 10 is a spectrum diagram showing an IR spectrum of a film produced in Example 5.

FIG. 11 is a spectrum diagram showing an IR spectrum of a film produced in Example 6.

FIG. 12 is a spectrum diagram showing an IR spectrum of a film produced in Example 7.

[Explanation of symbols]

 1 Vacuum container 2 Exhaust port 3 Substrate holder 4 Heater 5,6 Quartz tube 7 High frequency coil 8 Micro waveguide 9-12 Gas introduction tube

Claims (17)

[Claims] 1. At least hydrogen and III in the periodic table
A non-single-crystal optical semiconductor containing a group element and nitrogen, wherein an infrared absorption spectrum of the non-single-crystal optical semiconductor has an absorption peak (NH) indicating a bond between nitrogen and hydrogen, and a bond between carbon and hydrogen. Ratio of absorbance to indicated absorption peak (CH) I _NH / I
The ratio of the absorbance I _NH / of the absorption peak (NH) indicating a bond between nitrogen and hydrogen, where _CH is 3 or more, and the absorption peak (III-H) indicating a bond between a group III element and hydrogen. I
_III-H is 0.05 or more, and the absorption peak (III-N) indicating the bond between group III element and nitrogen and the absorption peak (III-H) indicating the bond between group III element and hydrogen, The absorbance ratio I _III-N / I _III-H is 1.5 or more, the absorption peak (III-N) is a single absorption band, and the half width of the absorption peak (III-N) is 250. A non-single-crystal optical semiconductor having a size of cm ^-1 or less. 2. The method according to claim 1, wherein the hydrogen content is at least 0.5 atomic% and at least 50 atomic%
The non-single-crystal optical semiconductor according to claim 1, which is included in the following range. 3. The ratio of the total number x of atoms of group III elements to the number y of nitrogen in the periodic table is from 1.0: 0.5 to 1.0: 1.0.
The non-single-crystal optical semiconductor according to claim 1, wherein the value is between 2.0 and 2.0. 4. A group III element in the periodic table, wherein A
The non-single-crystal optical semiconductor according to any one of claims 1 to 3, wherein the non-single-crystal optical semiconductor is at least one selected from the group consisting of l, Ga, and In. 5. The non-monolithic device according to claim 1, further comprising at least one element selected from the group consisting of C, Si, Ge, and Sn. Crystal optical semiconductor. 6. The method according to claim 1, further comprising at least one element selected from the group consisting of Be, Mg, Ca, Zn, and Sr. Non-single crystal optical semiconductor. 7. A non-single unit comprising reacting an active species having activated a compound containing nitrogen and an organometallic compound containing a Group III element in the periodic table in an atmosphere containing activated hydrogen. A method for manufacturing a crystalline optical semiconductor. 8. The method for producing a non-single-crystal optical semiconductor according to claim 7, wherein the activated hydrogen is supplied by activating a compound containing hydrogen. 9. The method for producing a non-single-crystal optical semiconductor according to claim 8, wherein the activated hydrogen is supplied by activating an organometallic compound. A high-frequency discharge and / or an activating means.
10. The method for manufacturing a non-single-crystal optical semiconductor according to claim 7, wherein a microwave discharge is used. 11. The non-single-crystal optical semiconductor according to claim 10, wherein at least one or more organometallic compounds containing a group III element in the periodic table are introduced from a downstream side of the activating means. Manufacturing method. 12. An electrophotographic photosensitive member, wherein the non-single-crystal optical semiconductor according to claim 1 is used as at least one of constituent materials. 13. The electrophotographic photoreceptor according to claim 12, wherein the non-single-crystal optical semiconductor according to claim 1 is used as a charge generation layer. 14. The electrophotographic photoreceptor according to claim 12, wherein the non-single-crystal optical semiconductor according to claim 1 is used as a charge transport layer. 15. The method according to claim 12, wherein the non-single-crystal optical semiconductor according to claim 1 is used as a surface layer. Electrophotographic photoreceptor. 16. A photovoltaic element comprising a non-single-crystal optical semiconductor according to any one of claims 1 to 6 laminated on a conductive substrate. 17. A light-receiving element comprising at least one layer of the non-single-crystal optical semiconductor according to claim 1 on a conductive substrate.